US3919181A - Preparation of hydrocarbon resins using zirconium tetrachloride - Google Patents
Preparation of hydrocarbon resins using zirconium tetrachloride Download PDFInfo
- Publication number
- US3919181A US3919181A US405455A US40545573A US3919181A US 3919181 A US3919181 A US 3919181A US 405455 A US405455 A US 405455A US 40545573 A US40545573 A US 40545573A US 3919181 A US3919181 A US 3919181A
- Authority
- US
- United States
- Prior art keywords
- styrene
- process according
- alpha
- limonene
- pinene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
- C08F4/16—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of silicon, germanium, tin, lead, titanium, zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/06—Hydrocarbons
Definitions
- ABSTRACT Styrene is homopolymerized 0r copolymerized with alpha methyl styrene. preferably in the presence of limonene. with or without t-butyl styrene. using zirconium tetrachloride as the catalyst.
- the light colored resins formed are useful as drying cleaning sizing agents and in hot melt adhesives.
- the present invention is directed to the making of copolymers of styrene with alpha-methyl styrene, or more preferably, terpolymers styrene with alpha-methyl styrene and a third monomer, most pref erably limonene.
- terpolymers styrene with alpha-methyl styrene
- a third monomer most pref erably limonene.
- terpenes such as alpha-pinene, beta-pinene or dipentene in place of all or part of the limonene.
- the limonene is employed as the more readily available d-limonene.
- terpene vinyl toluene e.g., p-vinyl toluene or t-butyl styrene, c.g., p-tbutyl styrene.
- styrene homopolymers as well as homopolymers of t-butyl styrene, d-limonene, alphamethyl styrene, etc.
- zirconium tetrachloride produces lightcolored resins with or without the d-limonene or other third monomer.
- t-butyl styrene When t-butyl styrene is present it generally yields a higher melting product.
- the tetrapolymer of styrene, t-butyl styrene, alpha-methyl styrene and d-limonene had a melting point of 125C, and the homopolymer of t-butyl styrene can be made with a melting point even above 155C.
- the zirconium tetrachloride is usually employed in an amount of 0.1 to 8% by weight of the total polymerizable monomers.
- the catalyst employed preferably consists of or consists essentially of the zirconium tetrachloride.
- the reaction can be carried out over a wide temperature range, e.g., 20 to 55C with 3035C being preferred.
- the temperature is not a critical feature of the invention.
- zirconium catalyst resins Another advantage of the zirconium catalyst resins is that these resins when compounded into a hot melt adhesive exhibit excellent heat age characteristics and in this respect were superior to boron fluoride catalyzed resins.
- the resins of the invention have utility as dry cleaning sizing agents which are utilized to give body to clothes after dry cleaning. They also are useful in hot melt adhesive compositions, particularly with paraffin wax and resinous ethylene-vinyl acetate copolymers. e.g., Elvax.
- Compatibility of the resins of the invention is controlled by the monomer composition of the resin.
- Styrene in general promotes incompatability with paraffin wax and ethylene vinyl acetate.
- Vinyl toluene and p-tbutyl styrene are more compatible than styrene, but not as compatible as limonene styrene.
- Terpenes such as those set forth above, e.g., d-limonene promote corn patibility as does alpha-methyl styrene.
- the polymers can also be molded to form cups.
- the optimum resin does not use a single monomer since styrene by itself produces a 100% yield of a much too incompatible water-white resin.
- Alpha-methyl styrene by itself produces a resin which has too low a melting point.
- d-Limonene also by itself produces a soft resin with a poor yield. In order to optimize compatibility, yield, and melting point it is necessary to judiciously select the proper monomers and ratios.
- terpolymers there is generally employed 5 to 50 by weight styrene, 5 to 80 alpha-methyl styrene and 5 to 50 7c of terpene, e.g., d-limonene or other third component.
- terpene e.g., d-limonene or other third component.
- tetrapolymers there is generally employed 5 to 50 7r styrene, 5 to 80 7: alphamethyl styrene, 5 to 60 terpene and 5 to 50 7r t-butyl styrene.
- solvents e.g., aromatic hydrocarbon such as xylene. benzene, toluene, or aliphatic hydrocarbons, e.g., heptane or mineral spirits.
- Example 1 A Alpha-methyl styrene 750grams B Styrene 250 C Xylene 650 D Zirconium tetrachloride 10 E Water F Water 100 G Water 100 spherically to 200C. yielding a water-white resin with a melting point of 103C. and a yield of 960 grams. (96%)
- Example 2 4 much increased resistance to color change and resis tance to skimming.
- the cloud point of a hot melt adhesive i.e., the temperature at which the molten adhesive becomes turbid, is controlled by the ratios of monomers in the resin. For example:
- Example 1 three-necked flask equipped as in Example 1. The temperature was brought to 30C. and Material E was added over minutes controlling the temperature at 35. The reaction proceeded for 1 hour at 30-35. Then material F was added. The mixture was stirred at 75C. for /5 hour. The layers were separated and the bottom water layer was removed. Material G was added and the resin solution was again washed and the water layer removed. Material H was similarly utilized to wash the resin solution The resin was then distilled atmospherically to 200C then steamed with indirect steam for 15 minutes. The yield was 950 grams (95%), MP was 120C, and the color was less than 1 on the Gardner Scale.
- Example 3 Hot Melt Adhesive Formulation A Paraffin Wax 25 parts B Resin 4() parts C Elvax 260' parts Ethylene vinyl acetate copnlymer. melt index [541). vinyl acetate content 2871. product of E l DuPont de Nemours Procedure Thermal Stability Studies Hot melt adhesives were prepared using the formulation of Example 3.
- Example 1 The resins of Examples 1 and 2 were compared with commercially available hot melt resins for resistance to thermal degradation showing their Example 4 A p-t-butyl styrene 750grams B Styrene 250 C Xylene 650 D Zirconium Tctrachloride 3.5 E Water F Water I00 G Water 100 The above formulation was processed in a similar manner to Example 1 yielding 997 grams of water white resin with a melting point of 155C.
- Example 5 A alpha methyl styrene 750grams B Styrene 250 C Heptane 650 D Zirconium Tetrachloride 5 E Water 100 F Water 100 G Water lot) The above formulation was processed in a similar manner to Example 1 yielding 978 grams of a water white polymer with a melting point of C.
- Example 6 A Styrene lUOOgrams B Xylene 650 C Zirconium Tetrachloride 5
- Example o-continued D Water I E Water I00 F Water I00 The above ingredients were processed in a similar manner to Example I yielding 1042 grams of a water white resin with a melting point of l 10C.
- Example 2 The above formulation was processed in a similar manner to Example 1 with A, B, C and D being placed in flask initially yielding 1011 grams of a water white resin with a melting point of 125C.
- the ranges of proportions of terpolymers and tetrapolymers can be varied at the will of the synthesizer. Normally the blends of monomers are selected to obtain whatever solubility parameter is desired. It is even possible to prepare viscous liquid polymers, e.g., homopolymers of d-limonene, which are useful as adhesives.
- a process of preparing a light colored aromatic vinyl resin comprising polymerizing a member of the group consisting of (1) as the sole monomer styrene, alpha-methyl styrene, alpha-pinene, beta-pinene, dipentene limonene or p-t-butyl styrene; (2) a mixture of (a) styrene and (b) alpha-methyl styrene; or (3) a mixture of (a) styrene, (b) alpha-methyl styrene and (c) as a third monomer a member of the group consisting of alpha-pinene, beta-pinene, dipentene limonene, p-tbutyl styrene and vinyl toluene; or (4) a mixture of (a) styrene, (b) alpha-methyl styrene, (c) polymerizable terpene selected
- a process according to claim 1 wherein the catalyst consists essentially of zirconium tetrachloride in an amount of 0.1 to 8% of the total monomers.
- a process according to claim 9 wherein said third monomer is alpha-pinene, beta-pinene, dipentene or limonene.
- a process according to claim 28 which is carried out in a aromatic hydrocarbon solvent.
- a process according to claim 28 which is carried out in xylene, benzene, toluene, heptane or mineral spirits as a solvent.
- a process according to claim 1 wherein the polymerization is carried out in an aromatic hydrocarbon solvent.
- the catalyst consists essentially of zirconium tetrachloride in an amount of 0.1 to 8% of the total monomers, and there is polymerized a mixture of (a) styrene, (b) alphamethyl styrene, (c) a polymerizable terpene selected from the group consisting of alpha-pinene, beta-pinene, dipentene and limonene and (d) p-t-butyl styrene.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerization Catalysts (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US405455A US3919181A (en) | 1973-10-11 | 1973-10-11 | Preparation of hydrocarbon resins using zirconium tetrachloride |
IT22903/74A IT1012605B (it) | 1973-10-11 | 1974-05-17 | Preparazione di resine idrocarburi che impiegando tetracloruro di zir conio |
ES427287A ES427287A1 (es) | 1973-10-11 | 1974-06-15 | Procedimiento para preparar una resina vinilica aromatica de color claro. |
DE2436842A DE2436842A1 (de) | 1973-10-11 | 1974-07-31 | Herstellung von vinylharzen |
ZA00745488A ZA745488B (en) | 1973-10-11 | 1974-08-27 | Preparation of hydrocarbon resins using zirconium tetrachloride |
AU72864/74A AU479411B2 (en) | 1973-10-11 | 1974-09-02 | Preparation of hydrocarbon resins using conium tetrachloride |
GB42699/74A GB1488010A (en) | 1973-10-11 | 1974-10-02 | Polymerisation of olefins using zirconium tetrachloride as catalyst |
JP11568174A JPS5736925B2 (it) | 1973-10-11 | 1974-10-09 | |
FR7434061A FR2247474B3 (it) | 1973-10-11 | 1974-10-10 | |
US05/825,051 USRE29654E (en) | 1973-10-11 | 1977-08-16 | Preparation of hydrocarbon resins using zirconium tetrachloride |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US405455A US3919181A (en) | 1973-10-11 | 1973-10-11 | Preparation of hydrocarbon resins using zirconium tetrachloride |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US05/825,051 Reissue USRE29654E (en) | 1973-10-11 | 1977-08-16 | Preparation of hydrocarbon resins using zirconium tetrachloride |
Publications (1)
Publication Number | Publication Date |
---|---|
US3919181A true US3919181A (en) | 1975-11-11 |
Family
ID=23603771
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US405455A Expired - Lifetime US3919181A (en) | 1973-10-11 | 1973-10-11 | Preparation of hydrocarbon resins using zirconium tetrachloride |
US05/825,051 Expired - Lifetime USRE29654E (en) | 1973-10-11 | 1977-08-16 | Preparation of hydrocarbon resins using zirconium tetrachloride |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US05/825,051 Expired - Lifetime USRE29654E (en) | 1973-10-11 | 1977-08-16 | Preparation of hydrocarbon resins using zirconium tetrachloride |
Country Status (8)
Country | Link |
---|---|
US (2) | US3919181A (it) |
JP (1) | JPS5736925B2 (it) |
DE (1) | DE2436842A1 (it) |
ES (1) | ES427287A1 (it) |
FR (1) | FR2247474B3 (it) |
GB (1) | GB1488010A (it) |
IT (1) | IT1012605B (it) |
ZA (1) | ZA745488B (it) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4394235A (en) * | 1980-07-14 | 1983-07-19 | Rj Archer Inc. | Heat-sealable polypropylene blends and methods for their preparation |
US5362316A (en) * | 1993-02-05 | 1994-11-08 | Imperbel America Corporation | Resinous cut-back compositions and methods of preparing the same |
US20160176999A1 (en) * | 2014-12-17 | 2016-06-23 | Toyo Tire & Rubber Co., Ltd. | Copolymer, rubber composition and pneumatic tire |
CN106008815A (zh) * | 2016-06-27 | 2016-10-12 | 梧州市嘉盈树胶有限公司 | 浅色萜烯树脂的制备方法 |
CN109824811A (zh) * | 2018-12-08 | 2019-05-31 | 濮阳班德路化学有限公司 | 一种α-甲基苯乙稀液体树脂的制备方法 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0638727U (ja) * | 1992-11-13 | 1994-05-24 | 株式会社関西製作所 | 寝台等における床部の昇降装置 |
US6982309B2 (en) * | 2003-12-19 | 2006-01-03 | Fina Technology, Inc. | Synthesis of branched styrenic copolymers with p-t-butylstyrene |
Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1939932A (en) * | 1931-03-30 | 1933-12-19 | Dayton Synthetic Chemicals Inc | Prepared resin |
US2060404A (en) * | 1932-06-15 | 1936-11-10 | Monsanto Petroleum Chemicals I | Decolorization of resins |
US2383084A (en) * | 1942-04-06 | 1945-08-21 | Hercules Powder Co Ltd | Terpene resins |
US2389240A (en) * | 1940-11-07 | 1945-11-20 | Phillips Petroleum Co | Process for the conversion of hydrocarbons |
US2436614A (en) * | 1942-07-10 | 1948-02-24 | Standard Oil Dev Co | Solid styrene polymer formation at low temperatures |
US2507338A (en) * | 1945-06-09 | 1950-05-09 | Atlantic Refining Co | Polymerization of alpha alkyl styrenes |
US2556488A (en) * | 1942-07-28 | 1951-06-12 | Sherwin Williams Co | Manufacture of polystyrene |
US3470145A (en) * | 1967-03-08 | 1969-09-30 | Geigy Chem Corp | Copolymers of alpha mono-olefins and terpenes |
US3478005A (en) * | 1966-04-27 | 1969-11-11 | Neville Chemical Co | Terpene copolymers |
US3640981A (en) * | 1969-04-23 | 1972-02-08 | Reichhold Chemicals Inc | Vinyl toluene-alpha methyl styrene co-polymers and method of preparing the same |
US3642636A (en) * | 1969-12-18 | 1972-02-15 | Chevron Res | Lubricating oil containing para-t-butyl-alpha-methylstyrene polymers |
US3654250A (en) * | 1969-11-17 | 1972-04-04 | Reichhold Chemicals Inc | Copolymers from para tertiary butyl styrene and alpha methyl styrene and method for producing same |
US3725506A (en) * | 1970-11-16 | 1973-04-03 | Basf Ag | Manufacture of copolymers of styrene and {60 -methylstyrene |
US3753961A (en) * | 1971-12-03 | 1973-08-21 | Goodyear Tire & Rubber | Resinous composition |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2682531A (en) | 1951-03-31 | 1954-06-29 | Standard Oil Dev Co | Zirconium tetrachloride-ether complexes as low temperature polymerization catalyst |
BE554475A (it) | 1954-08-16 | Du Pont | ||
US2931791A (en) | 1955-05-23 | 1960-04-05 | Exxon Research Engineering Co | Polymerization of hydrocarbons with catalyst of bf3 and bci3 |
GB853848A (en) | 1956-01-04 | 1960-11-09 | Ethyl Corp | Polymerization of olefins |
NL236098A (it) | 1958-02-14 | |||
US3158593A (en) | 1958-04-24 | 1964-11-24 | Monsanto Co | Aluminum chlorofluoride polymerization catalysts |
GB970374A (en) | 1961-04-14 | 1964-09-23 | Firestone Tire & Rubber Co | Polymerization process and catalysts |
-
1973
- 1973-10-11 US US405455A patent/US3919181A/en not_active Expired - Lifetime
-
1974
- 1974-05-17 IT IT22903/74A patent/IT1012605B/it active
- 1974-06-15 ES ES427287A patent/ES427287A1/es not_active Expired
- 1974-07-31 DE DE2436842A patent/DE2436842A1/de active Pending
- 1974-08-27 ZA ZA00745488A patent/ZA745488B/xx unknown
- 1974-10-02 GB GB42699/74A patent/GB1488010A/en not_active Expired
- 1974-10-09 JP JP11568174A patent/JPS5736925B2/ja not_active Expired
- 1974-10-10 FR FR7434061A patent/FR2247474B3/fr not_active Expired
-
1977
- 1977-08-16 US US05/825,051 patent/USRE29654E/en not_active Expired - Lifetime
Patent Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1939932A (en) * | 1931-03-30 | 1933-12-19 | Dayton Synthetic Chemicals Inc | Prepared resin |
US2060404A (en) * | 1932-06-15 | 1936-11-10 | Monsanto Petroleum Chemicals I | Decolorization of resins |
US2389240A (en) * | 1940-11-07 | 1945-11-20 | Phillips Petroleum Co | Process for the conversion of hydrocarbons |
US2383084A (en) * | 1942-04-06 | 1945-08-21 | Hercules Powder Co Ltd | Terpene resins |
US2436614A (en) * | 1942-07-10 | 1948-02-24 | Standard Oil Dev Co | Solid styrene polymer formation at low temperatures |
US2556488A (en) * | 1942-07-28 | 1951-06-12 | Sherwin Williams Co | Manufacture of polystyrene |
US2507338A (en) * | 1945-06-09 | 1950-05-09 | Atlantic Refining Co | Polymerization of alpha alkyl styrenes |
US3478005A (en) * | 1966-04-27 | 1969-11-11 | Neville Chemical Co | Terpene copolymers |
US3470145A (en) * | 1967-03-08 | 1969-09-30 | Geigy Chem Corp | Copolymers of alpha mono-olefins and terpenes |
US3640981A (en) * | 1969-04-23 | 1972-02-08 | Reichhold Chemicals Inc | Vinyl toluene-alpha methyl styrene co-polymers and method of preparing the same |
US3654250A (en) * | 1969-11-17 | 1972-04-04 | Reichhold Chemicals Inc | Copolymers from para tertiary butyl styrene and alpha methyl styrene and method for producing same |
US3642636A (en) * | 1969-12-18 | 1972-02-15 | Chevron Res | Lubricating oil containing para-t-butyl-alpha-methylstyrene polymers |
US3725506A (en) * | 1970-11-16 | 1973-04-03 | Basf Ag | Manufacture of copolymers of styrene and {60 -methylstyrene |
US3753961A (en) * | 1971-12-03 | 1973-08-21 | Goodyear Tire & Rubber | Resinous composition |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4394235A (en) * | 1980-07-14 | 1983-07-19 | Rj Archer Inc. | Heat-sealable polypropylene blends and methods for their preparation |
US5362316A (en) * | 1993-02-05 | 1994-11-08 | Imperbel America Corporation | Resinous cut-back compositions and methods of preparing the same |
US20160176999A1 (en) * | 2014-12-17 | 2016-06-23 | Toyo Tire & Rubber Co., Ltd. | Copolymer, rubber composition and pneumatic tire |
CN105713127A (zh) * | 2014-12-17 | 2016-06-29 | 东洋橡胶工业株式会社 | 共聚物、橡胶组合物及充气轮胎 |
US9708477B2 (en) * | 2014-12-17 | 2017-07-18 | Toyo Tire & Rubber Co., Ltd. | Copolymer, rubber composition and pneumatic tire |
CN105713127B (zh) * | 2014-12-17 | 2018-10-09 | 东洋橡胶工业株式会社 | 共聚物、橡胶组合物及充气轮胎 |
CN106008815A (zh) * | 2016-06-27 | 2016-10-12 | 梧州市嘉盈树胶有限公司 | 浅色萜烯树脂的制备方法 |
CN109824811A (zh) * | 2018-12-08 | 2019-05-31 | 濮阳班德路化学有限公司 | 一种α-甲基苯乙稀液体树脂的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
ES427287A1 (es) | 1976-09-16 |
USRE29654E (en) | 1978-05-30 |
AU7286474A (en) | 1976-03-04 |
IT1012605B (it) | 1977-03-10 |
ZA745488B (en) | 1976-04-28 |
FR2247474B3 (it) | 1977-07-22 |
GB1488010A (en) | 1977-10-05 |
DE2436842A1 (de) | 1975-04-17 |
JPS5736925B2 (it) | 1982-08-06 |
JPS5066587A (it) | 1975-06-04 |
FR2247474A1 (it) | 1975-05-09 |
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